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The dependence on lithium-ion batteries leads to a pressing demand for advanced cathode materials. We demonstrate a new concept of layered-rocksalt intergrown structure that harnesses the combined figures of merit from each phase, including high capacity of layered and rocksalt phases, good kinetics of layered oxide and structural advantage of rocksalt. Based on this concept, lithium nickel ruthenium oxide of a main layered structure (R[Formula: see text]m) with intergrown rocksalt (Fm[Formula: see text]m) is developed, which delivers a high capacity with good rate performance. The interwoven rocksalt structure successfully prevents the anisotropic structural change that is typical for layered oxide, enabling a nearly zero-strain operation upon high-capacity cycling. Furthermore, a design principle is successfully extrapolated and experimentally verified in a series of compositions. Here, we show the success of such layered-rocksalt intergrown structure exemplifies a new battery electrode design concept and opens up a vast space of compositions to develop high-performance intergrown cathode materials.

By altering the surface of LiNi 0.6 Mn 0.2 Co 0.2 O 2 (NMC622) we show that surface defects and contaminants dominate the outgassing and irreversible surface transformations during the first electrochemical cycle. To alter the surface defects and contaminants without changing the bulk structure of the NMC622, we perform mild methanol and water rinses, a water soak, a water rinse and subsequent heat treatment, as well as purposeful increase of the surface Li 2 CO 3 . By combining isotopic labeling; gas analysis; and peroxide, hydroxide, and carbonate titrations we observe that these alterations change the surface Li 2 CO 3 , surface hydroxides, and the local defects, which in turn alter the nature and extent of the outgassing to O 2 and CO 2 . Our results highlight that outgassing of Li-ion cathode materials is highly dependent on the synthesis and storage routes and comparison of varying compositions must take into account these differences to make any meaningful conclusions. We also show that simple rinsing procedures may be an effective route to controlling interfacial reactivity of Li-ion active materials.

The stability of modern lithium-ion batteries depends critically on an effective solid-electrolyte interphase (SEI), a passivation layer that forms on the carbonaceous negative electrode as a result of electrolyte reduction. However, a nanoscopic understanding of how the SEI evolves with battery aging remains limited due to the difficulty in characterizing the structural and chemical properties of this sensitive interphase. In this work, we image the SEI on carbon black negative electrodes using cryogenic transmission electron microscopy (cryo-TEM) and track its evolution during cycling. We find that a thin, primarily amorphous SEI nucleates on the first cycle, which further evolves into one of two distinct SEI morphologies upon further cycling: (1) a compact SEI, with a high concentration of inorganic components that effectively passivates the negative electrode; and (2) an extended SEI spanning hundreds of nanometers. This extended SEI grows on particles that lack a compact SEI and consists primarily of alkyl carbonates. The diversity in observed SEI morphologies suggests that SEI growth is a highly heterogeneous process. The simultaneous emergence of these distinct SEI morphologies highlights the necessity of effective passivation by the SEI, as large-scale extended SEI growths negatively impact lithium-ion transport, contribute to capacity loss, and may accelerate battery failure.

Solid alkali metal carbonates are universal passivation layer components of intercalation battery materials and common side products in metal-O 2 batteries, and are believed to form and decompose reversibly in metal-O 2 /CO 2 cells. In these cathodes, Li 2 CO 3 decomposes to CO 2 when exposed to potentials above 3.8 V vs. Li/Li + . However, O 2 evolution, as would be expected according to the decomposition reaction 2 Li 2 CO 3 →4 Li + +4 e - +2 CO 2 +O 2 , is not detected. O atoms are thus unaccounted for, which was previously ascribed to unidentified parasitic reactions. Here, we show that highly reactive singlet oxygen ( 1 O 2 ) forms upon oxidizing Li 2 CO 3 in an aprotic electrolyte and therefore does not evolve as O 2 . These results have substantial implications for the long-term cyclability of batteries: they underpin the importance of avoiding 1 O 2 in metal-O 2 batteries, question the possibility of a reversible metal-O 2 /CO 2 battery based on a carbonate discharge product, and help explain the interfacial reactivity of transition-metal cathodes with residual Li 2 CO 3 ., (© 2018 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.)

Recent research has explored combining conventional transition-metal redox with anionic lattice oxygen redox as a new and exciting direction to search for high-capacity lithium-ion cathodes. Here, we probe the poorly understood electrochemical activity of anionic oxygen from a material perspective by elucidating the effect of the transition metal on oxygen redox activity. We study two lithium-rich layered oxides, specifically lithium nickel metal oxides where metal is either manganese or ruthenium, which possess a similar structure and discharge characteristics, but exhibit distinctly different charge profiles. By combining X-ray spectroscopy with operando differential electrochemical mass spectrometry, we reveal completely different oxygen redox activity in each material, likely resulting from the different interaction between the lattice oxygen and transition metals. This work provides additional insights into the complex mechanism of oxygen redox and development of advanced high-capacity lithium-ion cathodes.

The role of residual lithium carbonate in the electrochemistry and outgassing of lithium transition-metal oxides (TMOs) has been largely overlooked. By combining in situ gas analysis, isotopic labeling, and a surface carbonate titration, we show that the presence of residual lithium carbonate (Li 2 CO 3 ) on the surface of both Ni-rich Li-stoichiometric (specifically LiNi 0.6 Mn 0.2 Co 0.2 O 2 ) and Li-rich (Li 1.2 Ni 0.15 Co 0.1 Mn 0.55 O 2 ) TMOs has a direct correlation with the amount of CO 2 and CO evolved and has a relationship with O 2  evolved from the TMO lattice on the first charge. By selectively isotopically labeling the residual surface Li 2 CO 3 , which remains in small quantities (∼0.1 wt %) after synthesis, and not the carbonate electrolyte, we further show that, up to 4.8 V vs Li/Li + on the first charge, carbonate electrolyte degradation negligibly contributes to gas evolution. These key conclusions warrant a reassessment of our notion of oxidative decomposition of carbonate electrolytes on TMO surfaces and, more generally, the reactivity of TMO surfaces. For the battery research community, our results highlight the importance of quantification of the surface contaminants and suggest that further research is needed to fully understand the long-term effects of trace surface Li 2 CO 3 .

The Li-air battery has received significant attention over the past decade given its high theoretical specific energy compared to competing energy storage technologies. Yet, numerous scientific challenges remain unsolved in the pursuit of attaining a battery with modest Coulombic efficiency and high capacity. In this Feature Article, we provide our current perspective on challenges facing the development of nonaqueous Li-O2 battery cathodes. We initially present a review on our understanding of electrochemical processes occurring at the nonaqueous Li-O2 cathode. Electrolyte and cathode instabilities and Li2O2 conductivity limitations are then discussed, and suggestions for future materials research development to alleviate these issues are provided.

Molecular wires show promise in nanoscale electronics, but the synthesis of uniform, long conductive molecules is a significant challenge. Deoxyribonucleic acid (DNA) of precise length, by contrast, is synthesized easily, but its conductivity over the distances required for nanoscale devices has not been explored. Here we demonstrate DNA charge transport (CT) over 34 nm in 100-mer monolayers on gold. Multiplexed gold electrodes modified with 100-mer DNA yield sizable electrochemical signals from a distal, covalent Nile Blue redox probe. Significant signal attenuation upon incorporation of a single base-pair mismatch demonstrates that CT is DNA-mediated. Efficient cleavage of these 100-mers by a restriction enzyme indicates that the DNA adopts a native conformation accessible to protein binding. Similar electron-transfer rates measured through 100-mer and 17-mer monolayers are consistent with rate-limiting electron tunnelling through the saturated carbon linker. This DNA-mediated CT distance of 34 nm surpasses that of most reports of molecular wires.